CN114592208A - Preparation method of nitrogen-doped graphitized modified electrode - Google Patents
Preparation method of nitrogen-doped graphitized modified electrode Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 216
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 104
- 229910052751 metal Inorganic materials 0.000 claims abstract description 54
- 239000002184 metal Substances 0.000 claims abstract description 54
- 238000004140 cleaning Methods 0.000 claims abstract description 41
- 239000000758 substrate Substances 0.000 claims abstract description 40
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 claims abstract description 22
- 230000007797 corrosion Effects 0.000 claims abstract description 20
- 238000005260 corrosion Methods 0.000 claims abstract description 20
- 238000006243 chemical reaction Methods 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 15
- 239000011259 mixed solution Substances 0.000 claims abstract description 10
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 9
- 238000005087 graphitization Methods 0.000 claims abstract description 8
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims abstract description 7
- 230000004048 modification Effects 0.000 claims abstract description 7
- 238000012986 modification Methods 0.000 claims abstract description 7
- 239000007787 solid Substances 0.000 claims abstract description 6
- 238000004729 solvothermal method Methods 0.000 claims abstract description 6
- 239000000463 material Substances 0.000 claims abstract description 5
- 239000000126 substance Substances 0.000 claims abstract description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 28
- 239000000243 solution Substances 0.000 claims description 22
- 238000001035 drying Methods 0.000 claims description 21
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 20
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 20
- 239000004519 grease Substances 0.000 claims description 19
- 239000012153 distilled water Substances 0.000 claims description 17
- 238000010438 heat treatment Methods 0.000 claims description 15
- 238000005406 washing Methods 0.000 claims description 14
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 13
- 239000001257 hydrogen Substances 0.000 claims description 13
- 229910052739 hydrogen Inorganic materials 0.000 claims description 13
- 239000006260 foam Substances 0.000 claims description 10
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 claims description 10
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 8
- 235000018660 ammonium molybdate Nutrition 0.000 claims description 7
- 239000011609 ammonium molybdate Substances 0.000 claims description 7
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims description 7
- 229940010552 ammonium molybdate Drugs 0.000 claims description 7
- 238000011049 filling Methods 0.000 claims description 7
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims description 6
- 229920000877 Melamine resin Polymers 0.000 claims description 6
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 5
- 239000002041 carbon nanotube Substances 0.000 claims description 5
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 5
- 229910052700 potassium Inorganic materials 0.000 claims description 5
- 239000011591 potassium Substances 0.000 claims description 5
- 235000003270 potassium fluoride Nutrition 0.000 claims description 5
- 239000011698 potassium fluoride Substances 0.000 claims description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 230000003197 catalytic effect Effects 0.000 claims description 4
- 238000005868 electrolysis reaction Methods 0.000 claims description 4
- 235000015393 sodium molybdate Nutrition 0.000 claims description 3
- 239000011684 sodium molybdate Substances 0.000 claims description 3
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 claims description 3
- 239000002923 metal particle Substances 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 238000001291 vacuum drying Methods 0.000 claims description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052750 molybdenum Inorganic materials 0.000 abstract description 2
- 239000011733 molybdenum Substances 0.000 abstract description 2
- 239000010410 layer Substances 0.000 description 27
- 230000000052 comparative effect Effects 0.000 description 10
- 238000009210 therapy by ultrasound Methods 0.000 description 8
- 238000010301 surface-oxidation reaction Methods 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 229910000510 noble metal Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 239000010411 electrocatalyst Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000002803 fossil fuel Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 2
- 229910005809 NiMoO4 Inorganic materials 0.000 description 1
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 description 1
- 241001494479 Pecora Species 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 239000003502 gasoline Substances 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Inorganic materials O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 239000002082 metal nanoparticle Substances 0.000 description 1
- VLAPMBHFAWRUQP-UHFFFAOYSA-L molybdic acid Chemical compound O[Mo](O)(=O)=O VLAPMBHFAWRUQP-UHFFFAOYSA-L 0.000 description 1
- 229910001453 nickel ion Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/055—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material
- C25B11/057—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material consisting of a single element or compound
- C25B11/061—Metal or alloy
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
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Abstract
The application discloses a preparation method of a nitrogen-doped graphitized modified electrode, which comprises the following steps of carrying out surface cleaning treatment on a metal nickel substrate to obtain a clean metal nickel substrate; performing corrosion treatment based on solvothermal reaction on the metal nickel substrate subjected to surface cleaning treatment in a mixed solution containing molybdate and fluoride; carrying out gas-solid reaction on the corroded metal nickel substrate under the protection of inert atmosphere, and carrying out nitrogen-doped graphitization modification on a substrate surface substance to obtain the nitrogen-doped graphitization modified electrode; compared with the traditional nickel-based electrode preparation method, the method has the advantages that molybdenum is introduced on the nickel substrate based on hydrothermal reaction to form a nano rod-shaped surface structure containing bimetal, and the specific surface area of the material is increased.
Description
Technical Field
The invention belongs to the technical field of cathode electrodes for electrolyzing water, and particularly relates to a preparation method of a nitrogen-doped graphitized modified electrode.
Background
The massive use of fossil fuels leads to increasingly serious environmental pollution problems and rapid exhaustion of fossil fuels, which affect daily life of people, so that exploring and developing sustainable clean energy to replace traditional fossil energy is a great problem to be solved urgently in the field of leading-edge scientific research.
Clean energy refers to a new energy technology capable of effectively reducing greenhouse gas emission, and is one of important methods for reducing carbon dioxide emission. The carbon-free hydrogen energy source becomes the first choice of clean energy, and the product of hydrogen combustion is water, which is the cleanest energy source in the world. And hydrogen has the characteristic of high combustion heat value, which is 3 times of gasoline, 3.9 times of alcohol and 4.5 times of coke. The current water electrolysis hydrogen production compatible with new energy (wind, light, water and electricity and the like) is gradually developed and becomes the most green hydrogen energy obtaining way, wherein the alkaline water electrolysis is expected to become a green large-scale hydrogen production leading sheep.
Alkaline electrolyzed water mainly consists of Hydrogen Evolution Reaction (HER; 2H)2O+2e-＝H2+2OH-,E0-0.83V vs SHE) and Oxygen Evolution (Oxygen Evolution Reaction, OER; 2OH-＝1/2O2+H2O+2e-,E00.4V vs SHE) two half-reactions. From the analysis of the theoretical potential difference, the total reaction (H) of the electrolyzed water2O＝H2+1/2O2；E01.23V vs SHE) is 1.23V. Currently, noble metal catalysts such as platinum-based materials and ruthenium dioxide are considered to be the most effective electrocatalysts for Hydrogen Evolution Reaction (HER) and Oxygen Evolution Reaction (OER). However, these noble metal catalysts are costly, have poor durability and are scarce and difficult to use commercially on a large scale. Accordingly, there has been a great deal of effort to explore stable, efficient, low cost non-noble metal materials.
In recent years, much new work has been around developing low cost alternative catalysts, mainly NiO, Ni (OH)2、 NiMoO4、Ni2P、MnO2And the like.
Disclosure of Invention
The technical problem to be solved is as follows:
aiming at the defects of the prior art, the method solves the technical problems that the existing noble metal catalyst is high in cost, poor in durability and rare, and difficult to implement large-scale commercial application, and the like, and provides a nitrogen-doped graphitized modified electrode preparation method.
The technical scheme is as follows:
in order to achieve the purpose, the application is realized by the following technical scheme:
a preparation method of a nitrogen-doped graphitized modified electrode comprises the following steps:
firstly, surface cleaning treatment: cleaning the surface of the metal nickel substrate to obtain a clean metal nickel substrate;
and step two, carrying out root molybdate corrosion treatment: performing corrosion treatment based on a solvothermal reaction on the metal nickel substrate subjected to the surface cleaning treatment in a mixed solution containing molybdate and fluoride;
thirdly, nitrogen doping graphitization modification treatment: and carrying out gas-solid reaction on the corroded metal nickel substrate under the protection of inert atmosphere, and carrying out nitrogen-doped graphitization modification on the surface substance of the substrate to obtain the nitrogen-doped graphitization modified electrode.
Furthermore, the nitrogen-doped graphitized modified electrode surface layer substance is a nitrogen-doped carbon nanotube and nano metal particles wrapped by the nitrogen-doped carbon nanotube, and shows high-efficiency alkaline environment water electrolysis hydrogen evolution catalytic performance.
Further, the metal nickel substrate is a 60-mesh plain nickel mesh, a nickel sheet or a foamed nickel.
Further, the surface cleaning treatment comprises the following specific steps: ultrasonic cleaning in acetone solution for 10-25min, repeatedly cleaning with ethanol to remove the grease layer on the metal surface, placing the metal nickel substrate with the grease layer on the metal surface removed in hydrochloric acid solution with the concentration of 1-5mol/L for ultrasonic cleaning for 5-15min, standing for 10-25min, repeatedly cleaning with distilled water to remove the oxide layer on the metal surface, and drying in an oven to obtain the clean metal nickel substrate.
Further, in the second step, the molybdate is one or more of 10-30mmol/L ammonium molybdate, 26mmol/L sodium molybdate and 16mmol/L potassium molybdate, and the fluoride is 24-48mmol/L potassium fluoride and/or 24-68mmol/L ammonium fluoride.
Further, the corrosion treatment based on the solvothermal reaction in the second step comprises the following specific steps: firstly, placing the metal nickel substrate subjected to surface cleaning treatment in a hydrothermal kettle containing a mixed solution of molybdate and fluoride, wherein the filling degree of the hydrothermal kettle is 40-90%, heating the hydrothermal kettle to 90-180 ℃, keeping the temperature for 1-20h, washing the metal nickel substrate subjected to hydrothermal reaction with distilled water, and drying to obtain the metal nickel substrate subjected to molybdate corrosion treatment.
Further, the third step is that the metal nickel substrate after corrosion treatment is placed in the middle section of the tube furnace under the protection of inert atmosphere, 0.08-2.4g of melamine is placed in the middle section of the tube furnace under the protection of inert atmosphere, the tube furnace is heated to 450-1200 ℃, the temperature is kept for 0.5-12h, the metal nickel substrate after heat treatment in the tube furnace is washed by ethanol, and the nitrogen-doped graphitized modified electrode is obtained through vacuum drying.
Has the advantages that:
the application provides a nitrogen-doped graphitized modified electrode preparation method, which has the following beneficial effects compared with the prior art:
1. compared with the traditional nickel-based electrode preparation method, molybdenum is introduced on a nickel substrate based on hydrothermal reaction to form a nano rod-shaped surface structure containing bimetal, so that the specific surface area of the material is improved;
2. based on gas-solid reaction, nickel and molybdenum metal nanoparticles coated by nitrogen-doped carbon nanotubes are formed on the surface of the material, so that the intrinsic catalytic activity is improved;
3. the preparation process is simple, external nickel ions do not need to be introduced, the cost is low, and the method is suitable for production and popularization;
4. the invention provides a preparation method of a nitrogen-doped graphitized modified electrode. Firstly prepares NiMoO through the solvothermal reaction4And (3) carrying out gas-solid reaction on the base electrode to prepare the nitrogen-doped graphitized modified electrode. The electrode exhibits a hydrogen evolution catalytic activity greatly improved as compared with a Ni-based electrode as a cathode for alkaline electrolyzed water. The alkaline hydrogen evolution reaction performance of the electrode of the embodiment obtained by adopting different metal nickel substrates is obviously improved compared with that of a comparative electrode based on an original metal substrate, particularly, the electrode prepared by adopting the foamed nickel has the overpotential absolute value of only 0.198 volt under the current density of 10 milliamperes per square centimeter, is reduced by 0.130 volt compared with a pure foamed nickel electrode, and is prepared into electricity by only surface cleaning treatment and molybdate root corrosion treatmentThe pole drops by 0.107 volts. Meanwhile, the overpotential of the electrode prepared by adopting the nickel foam is only raised by 2 millivolts after the continuous oxygen evolution reaction for 20 hours.
Drawings
Fig. 1 is a scanning electron microscope picture of a nitrogen-doped graphitized modified electrode prepared in example 4 of the present technology, where the left picture is a scanning electron microscope picture magnified by 5000 times and the right picture is a scanning electron microscope picture magnified by 100000 times.
Detailed Description
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Furthermore, it should be understood that various changes or modifications can be made by those skilled in the art after reading the teaching of the present invention, and equivalents also fall within the scope of the claims of the present application.
Example 1:
a method for preparing a nitrogen-doped graphitized modified electrode, which uses a nickel net as a metallic nickel substrate, comprises the following steps:
firstly, placing a 60-mesh plain nickel net in an acetone solution for ultrasonic cleaning for 15min, and repeatedly cleaning with ethanol to remove a grease layer on the surface of metal;
secondly, placing the nickel screen without the metal surface grease layer in a hydrochloric acid solution with the concentration of 2mol/L for ultrasonic treatment for 15min, standing for 15min, repeatedly cleaning with distilled water, removing the metal surface oxidation layer, and drying to obtain the nickel screen after surface cleaning treatment;
thirdly, placing the nickel screen subjected to surface cleaning treatment in a hydrothermal kettle containing a mixed solution of 10mmol/L ammonium molybdate, 16mmol/L potassium molybdate and 48mmol/L potassium fluoride, wherein the filling degree of the reaction kettle is 40%, heating the hydrothermal kettle to 120 ℃, and keeping the temperature for 15 hours;
fourthly, washing the nickel net subjected to the hydrothermal reaction by distilled water and drying to obtain the nickel net subjected to the molybdic acid root corrosion treatment;
the fifth step: putting a nickel net with the size of 4 square centimeters and subjected to root-molybdate corrosion treatment and 0.8g of melamine in the middle section of a tube furnace under the protection of inert atmosphere, heating the tube furnace to 700 ℃, and keeping the temperature for 8 hours;
and a sixth step: and washing the nickel net subjected to the heat treatment in the tube furnace by using ethanol and drying in vacuum to obtain the nitrogen-doped graphitized modified electrode.
Example 2:
a method for preparing a nitrogen-doped graphitized modified electrode, which uses foamed nickel as a metallic nickel substrate, comprises the following steps:
firstly, putting the foamed nickel into an acetone solution for ultrasonic cleaning for 10min, and then repeatedly cleaning the foamed nickel by using ethanol to remove a metal surface grease layer;
secondly, placing the foamed nickel with the metal surface grease layer removed in a hydrochloric acid solution with the concentration of 3mol/L for ultrasonic treatment for 10min, standing for 20min, repeatedly cleaning with distilled water, removing the metal surface oxide layer, and drying to obtain the foamed nickel with the surface cleaned;
thirdly, placing the foamed nickel subjected to surface cleaning treatment into a hydrothermal kettle containing a mixed solution of 20mmol/L ammonium molybdate, 26mmol/L sodium molybdate and 68mmol/L ammonium fluoride, wherein the filling degree of the reaction kettle is 80%, heating the hydrothermal kettle to 150 ℃, and keeping the temperature for 6 hours;
fourthly, washing the foam nickel subjected to the hydrothermal reaction with distilled water and drying to obtain the foam nickel subjected to the molybdate corrosion treatment;
the fifth step: placing 4 square centimeters of foamed nickel subjected to root-molybdate corrosion treatment in the middle section of the tubular furnace under the protection of inert atmosphere, placing 2.4 grams of melamine in the middle section of the tubular furnace under the protection of inert atmosphere, heating the tubular furnace to 1200 ℃, and keeping the temperature for 0.5 hour;
and a sixth step: and washing the foamed nickel subjected to the heat treatment in the tube furnace with ethanol and drying in vacuum to obtain the nitrogen-doped graphitized modified electrode.
Example 3
A method for preparing a nitrogen-doped graphitized modified electrode, which uses a nickel sheet as a metallic nickel substrate, comprises the following steps:
firstly, putting a nickel sheet into an acetone solution, ultrasonically cleaning for 20min, and repeatedly cleaning with ethanol to remove a metal surface grease layer;
secondly, placing the nickel sheet with the metal surface grease layer removed in a hydrochloric acid solution with the concentration of 1mol/L for ultrasonic treatment for 20min, standing for 10min, repeatedly cleaning with distilled water, removing the metal surface oxidation layer, and drying to obtain the nickel sheet with the surface cleaned;
thirdly, placing the nickel sheet subjected to surface cleaning treatment in a hydrothermal kettle containing a mixed solution of 10mmol/L ammonium molybdate and 56mmol/L ammonium fluoride, wherein the filling degree of the reaction kettle is 90%, heating the hydrothermal kettle to 90 ℃, and keeping the hydrothermal kettle for 20 hours;
fourthly, washing the nickel sheet after the hydrothermal reaction by distilled water and drying to obtain the nickel sheet after the corrosion treatment of the molybdate root;
the fifth step: placing a nickel sheet which is 4 square centimeters and is subjected to root-molybdate corrosion treatment in the middle section of the tubular furnace under the protection of inert atmosphere, placing 0.08g of melamine in the middle section of the tubular furnace under the protection of inert atmosphere, adding the tubular furnace to 450 ℃, and keeping for 12 hours;
and a sixth step: and washing the nickel sheet subjected to the heat treatment in the tube furnace by using ethanol and drying in vacuum to obtain the nitrogen-doped graphitized modified electrode.
Example 4
A method for preparing a nitrogen-doped graphitized modified electrode, which uses foamed nickel as a metallic nickel substrate, comprises the following steps:
firstly, putting the foamed nickel into an acetone solution for ultrasonic cleaning for 25min, and then repeatedly cleaning the foamed nickel with ethanol to remove a metal surface grease layer;
secondly, placing the foamed nickel with the metal surface grease layer removed in a hydrochloric acid solution with the concentration of 5mol/L for ultrasonic treatment for 5min, standing for 25min, repeatedly cleaning with distilled water, removing the metal surface oxidation layer, and drying to obtain the foamed nickel with the surface cleaned;
thirdly, placing the foamed nickel subjected to the surface cleaning treatment into a solution containing 30mmol/L ammonium molybdate, 16mmol/L potassium molybdate,
Heating a hydrothermal kettle containing 24mmol/L potassium fluoride and 24mmol/L ammonium fluoride mixed solution to 180 ℃ with the reaction kettle filling degree of 60%, and keeping the temperature for 1 h;
fourthly, washing the foam nickel subjected to the hydrothermal reaction with distilled water and drying to obtain the foam nickel subjected to the molybdate corrosion treatment;
the fifth step: placing 4 square centimeters of foamed nickel subjected to root-molybdate corrosion treatment in the middle section of the tubular furnace under the protection of inert atmosphere, placing 3.2 grams of melamine in the middle section of the tubular furnace under the protection of inert atmosphere, adding the tubular furnace to 950 ℃, and keeping for 4 hours;
and a sixth step: and washing the foamed nickel subjected to the heat treatment in the tube furnace with ethanol and drying in vacuum to obtain the nitrogen-doped graphitized modified electrode.
Comparative example 1
This comparative example directly used a 60 mesh plain nickel mesh as the electrode:
placing the 60-mesh plain nickel screen in an acetone solution, ultrasonically cleaning for 15min, and repeatedly cleaning with ethanol to remove an oil layer on the surface of the nickel screen; s12, placing the nickel screen with the surface grease layer removed in a hydrochloric acid solution with the concentration of 2mol/L for ultrasonic treatment for 15min, standing for 15min, repeatedly washing with distilled water, removing the metal surface oxide layer, and drying to obtain the clean nickel screen.
Comparative example 2:
this comparative example directly used foamed nickel as the electrode:
placing the foamed nickel in an acetone solution, ultrasonically cleaning for 25min, and repeatedly cleaning with ethanol to remove the grease layer on the surface of the foamed nickel; s12, placing the nickel foam with the surface grease layer removed in a hydrochloric acid solution with the concentration of 5mol/L for 5min by ultrasonic treatment, standing for 25min, repeatedly washing with distilled water, removing the metal surface oxidation layer, and drying to obtain the clean nickel foam.
Comparative example 3:
this comparative example directly used a nickel plate as the electrode:
placing the nickel sheet in an acetone solution, ultrasonically cleaning for 10min, repeatedly cleaning with ethanol, and removing the grease layer on the surface of the nickel sheet; s12, placing the nickel sheet with the surface grease layer removed in a hydrochloric acid solution with the concentration of 1mol/L for ultrasonic treatment for 20min, standing for 10min, repeatedly washing with distilled water, removing the metal surface oxide layer, and drying to obtain the clean nickel sheet.
Comparative example 4:
in the comparative example, foamed nickel was used as a metallic nickel substrate, and only surface cleaning treatment and root molybdate etching treatment were used to prepare an electrode:
firstly, putting the foamed nickel into an acetone solution for ultrasonic cleaning for 25min, and then repeatedly cleaning the foamed nickel with ethanol to remove a metal surface grease layer;
secondly, placing the foamed nickel with the metal surface grease layer removed in a hydrochloric acid solution with the concentration of 5mol/L for ultrasonic treatment for 5min, standing for 25min, repeatedly cleaning with distilled water, removing the metal surface oxidation layer, and drying to obtain the foamed nickel with the surface cleaned;
thirdly, placing the foamed nickel subjected to surface cleaning treatment into a hydrothermal kettle containing a mixed solution of 30mmol/L ammonium molybdate, 16mmol/L potassium molybdate, 24mmol/L potassium fluoride and 24mmol/L ammonium fluoride, wherein the filling degree of the reaction kettle is 60%, heating the hydrothermal kettle to 180 ℃, and keeping the hydrothermal kettle for 1 h;
and fourthly, washing the foam nickel subjected to the hydrothermal reaction with distilled water and drying to obtain the foam nickel subjected to the molybdate corrosion treatment.
TABLE 1
Analysis table for hydrogen evolution performance of electrocatalyst in technical example and comparative example
The above-mentioned embodiments are intended to illustrate the objects, technical solutions and advantages of the present invention in further detail, and it should be understood that the above-mentioned embodiments are only exemplary embodiments of the present invention, and are not intended to limit the present invention, and any modifications, equivalents, improvements and the like made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (7)
1. A preparation method of a nitrogen-doped graphitized modified electrode is characterized by comprising the following steps: the method comprises the following steps:
firstly, surface cleaning treatment: cleaning the surface of the metal nickel substrate to obtain a clean metal nickel substrate;
and step two, carrying out root molybdate corrosion treatment: performing corrosion treatment based on a solvothermal reaction on the metal nickel substrate subjected to the surface cleaning treatment in a mixed solution containing molybdate and fluoride;
thirdly, nitrogen doping graphitization modification treatment: and carrying out gas-solid reaction on the corroded metal nickel substrate under the protection of inert atmosphere, and carrying out nitrogen-doped graphitization modification on the surface substance of the substrate to obtain the nitrogen-doped graphitization modified electrode.
2. The method for preparing the nitrogen-doped graphitized modified electrode according to claim 1, characterized in that: the nitrogen-doped graphitized modified electrode surface material is a nitrogen-doped carbon nanotube and nano metal particles wrapped by the nitrogen-doped carbon nanotube, and shows efficient catalytic performance of water electrolysis hydrogen evolution in an alkaline environment.
3. The method for preparing the nitrogen-doped graphitized modified electrode according to claim 1, characterized in that: the metal nickel substrate is 60-mesh plain nickel mesh, nickel sheet or foam nickel.
4. The method for preparing a nitrogen-doped graphitized modified electrode according to claim 1, characterized in that: the surface cleaning treatment comprises the following specific steps: ultrasonic cleaning in acetone solution for 10-25min, repeatedly cleaning with ethanol to remove the grease layer on the metal surface, placing the metal nickel substrate with the grease layer on the metal surface removed in hydrochloric acid solution with the concentration of 1-5mol/L for ultrasonic cleaning for 5-15min, standing for 10-25min, repeatedly cleaning with distilled water to remove the oxide layer on the metal surface, and drying in an oven to obtain the clean metal nickel substrate.
5. The method for preparing a nitrogen-doped graphitized modified electrode according to claim 1, characterized in that: in the second step, molybdate is one or more of 10-30mmol/L ammonium molybdate, 26mmol/L sodium molybdate and 16mmol/L potassium molybdate, and fluoride is 24-48mmol/L potassium fluoride and/or 24-68mmol/L ammonium fluoride.
6. The method for preparing a nitrogen-doped graphitized modified electrode according to claim 1, characterized in that: the corrosion treatment based on the solvothermal reaction in the second step comprises the following specific steps: firstly, placing the metal nickel substrate subjected to surface cleaning treatment in a hydrothermal kettle containing a mixed solution of molybdate and fluoride, wherein the filling degree of the hydrothermal kettle is 40-90%, heating the hydrothermal kettle to 90-180 ℃, keeping the temperature for 1-20h, washing the metal nickel substrate subjected to hydrothermal reaction with distilled water, and drying to obtain the metal nickel substrate subjected to molybdate corrosion treatment.
7. The method for preparing a nitrogen-doped graphitized modified electrode according to claim 1, characterized in that: and in the third step, the gas-solid reaction is to place the corroded metal nickel substrate in the middle section of the tubular furnace under the protection of inert atmosphere, place 0.08-2.4g of melamine in the middle section of the tubular furnace under the protection of inert atmosphere, heat the tubular furnace to 450-1200 ℃, keep the temperature for 0.5-12h, rinse the metal nickel substrate after the heat treatment of the tubular furnace with ethanol, and carry out vacuum drying to obtain the nitrogen-doped graphitized modified electrode.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111013635A (en) * | 2020-01-08 | 2020-04-17 | 河北大学 | Substrate-loaded nitrogen-doped carbon nanotube-surrounded molybdenum carbide particle composite material and preparation method and application thereof |
| CN111841593A (en) * | 2020-08-27 | 2020-10-30 | 中国地质大学（武汉） | Molybdenum carbide-based catalyst, preparation method and application |
| CN113249735A (en) * | 2021-04-19 | 2021-08-13 | 北京化工大学 | Preparation method of efficient molybdenum carbide hydrogen evolution catalyst |
| CN113846343A (en) * | 2021-07-17 | 2021-12-28 | 北京工业大学 | Preparation method of nickel-molybdenum carbide electrocatalyst |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111013635A (en) * | 2020-01-08 | 2020-04-17 | 河北大学 | Substrate-loaded nitrogen-doped carbon nanotube-surrounded molybdenum carbide particle composite material and preparation method and application thereof |
| CN111841593A (en) * | 2020-08-27 | 2020-10-30 | 中国地质大学（武汉） | Molybdenum carbide-based catalyst, preparation method and application |
| CN113249735A (en) * | 2021-04-19 | 2021-08-13 | 北京化工大学 | Preparation method of efficient molybdenum carbide hydrogen evolution catalyst |
| CN113846343A (en) * | 2021-07-17 | 2021-12-28 | 北京工业大学 | Preparation method of nickel-molybdenum carbide electrocatalyst |
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